Thermal ink jet ink composition

ABSTRACT

A thermal ink jet ink composition includes one or more volatile organic solvents, one or more humectants, one or more binder resins, one or more dyes, and one or both of a surfactant and a plasticizer. The one or more volatile organic solvents are selected from C 1 -C 4  alcohols, C 3 -C 6  ketones, C 4 -C 8  ethers, C 3 -C 6  esters, and mixtures thereof. The one or more humectants are present in an amount not more than 30% by weight of the ink jet ink composition. The ink jet ink composition optionally includes water up to 10% by weight of the ink jet ink composition.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of U.S. application Ser. No.12/059,753 filed Mar. 31, 2008 now U.S. Pat. No. 8,142,558, the contentsof which are incorporated herein by reference in its entirety.

BACKGROUND OF THE INVENTION

Thermal ink jet (TIJ) print heads produce ink droplets from thermalvaporization of the ink solvent. In the jetting process, a resistor isheated rapidly to produce a vapor bubble which subsequently ejects adroplet from the orifice. This process is extremely efficient andreproducible. Modern TIJ print heads for industrial graphicsapplications are capable of generating uniform drops of 4 pL or smallerin volume at frequencies of 36 kHz or greater. Typical commercial TIJdevices are specifically designed to vaporize water or solvents thathave physical properties close to those of water (e.g. high boilingpoint, large heat capacity, low molecular weight).

Although TIJ printing systems have been available for over 30 years,nearly all of the commercial inks available for thermal ink jet systemshave been water-based, i.e. they contain more than 50% water. Suchaqueous inks have one or more drawbacks such as long ink dry times orpoor adhesion to semi-porous or non-porous substrates.

There is a desire for inks with attractive performance characteristicssuch as short dry times, long decap times and good adhesion when using aTIJ system to print onto semi-porous and non-porous substrates.

BRIEF SUMMARY OF THE INVENTION

The invention provides a thermal ink jet ink composition including oneor more volatile organic solvents, one or more humectants, one or morebinder resins, and one or more dyes. In an embodiment, the humectantsare present in an amount not more than 30% by weight of the ink jet inkcomposition.

In another embodiment, the thermal ink jet ink composition includes oneor more volatile organic solvents, one or more humectants, one or morebinder resins, one or more dyes, and one or both of a surfactant and aplasticizer. The one or more volatile organic solvents are selected fromC₁-C₄ alcohols, C₃-C₆ ketones, C₄-C₈ ethers, C₃-C₆ esters, and mixturesthereof. The one or more humectants are present in an amount not morethan 30% by weight of the ink jet ink composition. The ink jet inkcomposition optionally includes water up to 10% by weight of the ink jetink composition.

The disclosure also provides a method for printing images on a substratein a thermal ink jet printer including directing droplets of the thermalink jet ink composition of the invention to a substrate and allowing theink droplets to dry, thereby printing images on a substrate.

The thermal ink jet ink composition of the invention has one or more ofthe following features: short dry times, long decap times, good adhesionto substrates, safety, and material compatibility. Decap time is definedas the amount of time a nozzle can remain dormant and then be firedagain without detrimental effect on the droplet velocity, weight ordirection. Fluids with good material compatibility are defined as thosewhich do not degrade the ability of the TIJ cartridge to fire for somereasonable length of time. The thermal ink jet ink composition does notrequire heat assist (e.g., thermal driers) when printed on semi-porousand non-porous substrates.

DETAILED DESCRIPTION OF THE INVENTION

The invention provides a thermal ink jet ink composition comprising oneor more volatile organic solvents, one or more humectants, one or morebinder resins, and one or more colorants.

In an embodiment, the invention provides a thermal ink jet inkcomposition comprising one or more volatile organic solvents, one ormore humectants, one or more binder resins, and one or more dyes,wherein the humectants are present in an amount not more than 30% byweight of the ink jet ink composition, wherein the one or more volatileorganic solvents are selected from the group consisting of C₁-C₄alcohols, C₄-C₈ ethers, C₃-C₆ ketones, C₃-C₆ esters, and mixturesthereof.

In another embodiment, the invention provides a thermal ink jet inkcomposition comprising one or more C₁-C₄ alcohols, one or morehumectants, one or more binder resins, one or more colorants, and one ormore plasticizers, wherein the plasticizers are present in an amount notmore than 5% by weight of the ink jet ink composition and are selectedfrom the group consisting of butyl benzyl phthalate, n-ethyl o,p-toluenesulfonamide, and mixtures thereof.

In yet another embodiment, the invention provides a thermal ink jet inkcomposition comprising one or more volatile organic solvents, one ormore humectants, one or more binder resins, one or more pigments,wherein the humectants are present in an amount not more than 30% byweight of the ink jet ink composition and the ink jet ink composition isfree or substantially free of a polymeric surfactant, wherein the one ormore volatile organic solvents are selected from the group consisting ofC₁-C₄ alcohols, C₄-C₈ ethers, C₃-C₆ ketones, C₃-C₆ esters, and mixturesthereof.

In accordance with an embodiment, the volatile organic solvents areselected from the group consisting of C₁-C₄ alcohols, C₄-C₈ ethers,C₃-C₆ ketones, C₃-C₆ esters, and mixtures thereof. Examples of C₁-C₄alcohols include methanol, ethanol, 1-propanol, and 2-propanol. Examplesof C₄-C₈ ethers include diethyl ether, dipropyl ether, dibutyl ether andtetrahydrofuran. Examples of C₃-C₆ ketones include acetone, methyl ethylketone and cyclohexanone. Examples of C₃-C₆ esters include methylacetate, ethyl acetate and n-butyl acetate. The organic solvents,particularly alcohols, ketones, and esters, have an attractive featurethat they penetrate semi- and non-porous substrate surfaces more readilythan water based inks, thus reducing dry time and improving adhesion.

The one or more volatile organic solvents can be present in any suitableamount, for example, in an amount 50% or more, about 60% or more, about70% or more, about 80% or more, or about 90% or more by weight of theink jet ink composition. In an embodiment, the one or more volatileorganic solvents can be present in an amount from 50 to about 99%,preferably from about 60 to about 97%, and more preferably from about 80to about 95% of the ink jet ink composition. The thermal ink jet inkcomposition of the invention can optionally include water in a suitableamount, e.g., up to 49% by weight, up to about 25% by weight, or up toabout 10% by weight, up to about 5% by weight, or up to about 2% byweight of the ink jet ink composition.

The thermal ink jet ink composition of the invention can include anysuitable colorant or colorants, which may be dye or pigment. In anembodiment of the invention, one or more dyes are employed as thecolorant, wherein the one or more dyes are selected from the groupconsisting of acid dyes, basic dyes, solvent dyes, disperse dyes,mordant dyes and any combination thereof. Examples of solvent dyesinclude naphthol dyes, azo dyes, metal complex dyes, anthraquinone dyes,quinoimine dyes, indigoid dyes, benzoquinone dyes, carbonium dyes,naphthoquinone dyes, naphthalimide dyes, phthalocyanine dyes, andperylene dyes.

For example, the thermal ink jet ink composition can include one or moredyes are selected from the group consisting of C.I. Solvent Yellow 19,C.I. Solvent Yellow 21, C.I. Solvent Yellow 61, C.I. Solvent Yellow 80,C.I. Solvent Orange 1, C.I. Orange 37, C.I. Orange 40, C.I. SolventOrange 54, C.I. Solvent Orange 63, C.I. Solvent Red 8, Solvent Red 49,C.I. Solvent Red 81, C.I. Solvent Red 82, C.I. Solvent Red 84, C.I.Solvent Red 100, C.I. Acid Red 92, C. I. Reactive red 31, Orient Pink312, C.I. Basic Violet 3, C.I. Basic Violet 4, C.I. Solvent Violet 8,C.I. Solvent Violet 21, C.I. Solvent Blue 2, C.I. Solvent Blue 5, C.I.Solvent Blue 11, C.I. Solvent Blue 25, C.I. Solvent Blue 36, C.I.Solvent Blue 38, C.I. Solvent Blue 55; C.I. Solvent Blue 70, C.I.Solvent Green 3, C.I. Solvent Black 3, C.I. Solvent Black 5, C.I.Solvent Black 7, C.I. Solvent Black 22, Solvent Black 26, C.I. SolventBlack 27 (MORFAST BLACK 101), C.I. Solvent Black 29 (VALIFAST BLACK3808), C.I. Acid Black 123, C.I. Solvent Black 48, C.I. Oil Blue 613,and any combination thereof, and preferably one or more dyes selectedfrom the group consisting of C.I. Solvent Black 29 (ORASOL BLACK RLI™),C.I. Solvent Black 26, C.I. Solvent Black 48, C.I. Solvent Black 3 (OilBlack 860), C.I. Basic Violet 3, C.I. Solvent Blue 38, C.I. Solvent Blue70, C.I. Oil Blue 613, C.I. Solvent Red 49 (ORIENT PINK™ 312), C.I.Solvent Orange 54 (VALIFAST ORANGE™ 3210), and any combination thereof.

Any suitable pigment can be used, for example, one or more pigmentsselected from the group consisting of phthalocyanine blue, carbon black,mars black, quinacridone magenta, ivory black, prussian blue, cobaltblue, ultramarine blue, manganese blue, cerulean blue, indathrone blue,chromium oxide, viridian, cobalt green, terre verte, nickel azo yellow,light green oxide, phthalocyanine green-chlorinated copperphthalocyanine, burnt sienna, perinone orange, irgazin orange,quinacridone magenta, cobalt violet, ultramarine violet, manganeseviolet, dioxazine violet, zinc white, titanium white, flake white,aluminum hydrate, blanc fixe, china clay, lithophone, arylide yellow G,arylide yellow 10G, barium chromate, chrome yellow, chrome lemon, zincyellow, cadmium yellow, aureolin, naples yellow, nickel titanate,arylide yellow GX, isoindolinone yellow, flavanthrone yellow, yellowochre, chromophthal yellow 8GN, toluidine red, quinacridone red,permanent crimson, rose madder, alizarin crimson, vermilion, cadmiumred, permanent red FRG, brominated anthranthrone, naphthol carbamide,perylene red, quinacridone red, chromophthal red BRN, chromophthalscarlet R, aluminum oxide, barium oxide, bismuth oxide, boric oxide,cadmium oxide, calcium oxide, cerium oxide, chromium oxide, cobaltoxide, copper oxide, iridium oxide, lead oxide, magnesium oxide,manganese oxide, nickel oxide, phosphorus oxide, potassium oxide,rutile, silicon oxide, silver oxide, sodium oxide, strontium oxide, tinoxide, titanium oxide, vanadium oxide, zinc oxide, zirconium oxide, andany combination thereof.

In embodiments, the pigments are selected from the group consisting ofazo pigments, phthalocyanine pigments, quinacridone pigments, dioxazinepigments, isoindolinone pigments, metal oxide pigments, carbon black,and any combination thereof.

The pigments can have any suitable particle size, for example, fromabout 0.005 micron to about 15 microns, preferably from about 0.005 toabout 1 micron, and more preferably from about 0.01 to about 0.3 micron.

In any of the embodiments above, the colorant, dye or pigment, can bepresent in an amount from about 0.01% to about 10%, preferably fromabout 0.5% to about 7%, and more preferably from about 1% to about 5% byweight of the ink jet ink composition.

In any of the embodiments above, any suitable humectant can be used.Preferably, humectants have a boiling point greater than 150° C.,greater than 200° C., or greater than 250° C., and/or a relativeevaporation rate less than 1.0, less than 0.9, less than 0.7, less than0.4, less than 0.1, or less than 0.01. The humectants typically aresolvents having one or more polar functional groups such as hydroxyl,ether, amide, ester, ketone, and carbonate, for example, two functionalgroups, which may be the same or different, such as two hydroxyl groupsor one hydroxyl group and one ether group. In an embodiment, the one ormore humectants are selected from the group consisting of polyol, glycolether, diacetone alcohol, 2-pyrrolidinone, N-methylpyrrolidinone, ethyllactate, propylene carbonate, 1,3-dimethyl-2-imidazolidindione, andalkyl esters, and any combination thereof.

For example, the polyol is selected from the group consisting ofpolyethylene glycol, polypropylene glycol, poly(ethylene-co-propyleneglycol), polyvinyl alcohol, trimethylol propane, ethylene glycol,glycerin, diethylene glycol, triethylene glycol, tripropylene glycol,tetraethylene glycol, pentaethylene glycol, 1,2-propylene glycol,1,3-propanediol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol,thiodiglycol, hexylene glycol, bis-2-hydroxyethyl ether, 1,4-butanediol,1,2-butenediol, 1,4-butenediol, 1,3-butenediol, 1,5-pentanediol,2,4-pentanediol, 2,4-heptanediol, 1,8-octanediol, 1,10-decanediol,1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol,1,2-bis(hydroxymethyl)cyclohexane, 1,2-bis(hydroxyethyl)-cyclohexane,3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, neopentylglycol, pentaerythritol, sorbitol, mannitol, and any combinationthereof, and preferably the polyol is selected from the group consistingof polyethylene glycol, trimethylol propane, ethylene glycol, glycerin,diethylene glycol, tripropylene glycol, and any combination thereof,

A preferred humectant is glycol ether, for example, a glycol etherselected from the group consisting of ethylene glycol monomethyl ether,ethylene glycol monoethyl ether, propylene glycol monomethyl ether,tripropylene glycol monomethyl ether, ethylene glycol monobutyl ether,diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,propylene glycol n-propyl ether, propylene glycol t-butyl ether,propylene glycol n-butyl ether, dipropylene glycol methyl ether,dipropylene glycol n-propyl ether, dipropylene glycol t-butyl ether,dipropylene glycol n-butyl ether, tripropylene glycol n-propyl ether,tripropylene glycol t-butyl ether, tripropylene glycol n-butyl ether,ethyl cellosolve, methyl cellosolve, polyethylene glycol monomethylether, polypropylene glycol monomethyl ether, methoxytriglycol,ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, and anycombination thereof, and preferably, the glycol ether is selected fromthe group consisting of ethylene glycol monomethyl ether, ethyleneglycol monoethyl ether, propylene glycol monomethyl ether, tripropyleneglycol monomethyl ether, ethylene glycol monobutyl ether, diethyleneglycol monomethyl ether, diethylene glycol monoethyl ether, and anycombination thereof. In embodiments of the invention, propylene glycolmonomethyl ether is a preferred humectant.

Humectants contribute, at least in part, to a feature of the thermal inkjet ink composition. Thus, humectants can lengthen decap times; however,excessive amounts of humectants could increase the dry time of the inkjet ink composition. In any of the embodiments, the one or morehumectants can be present in any suitable amount, for example, in anamount about 50% by weight or less, about 40% by weight or less,preferably about 30% by weight or less, about 25% by weight or less,about 20% by weight or less, about 15% by weight or less, or about 10%by weight or less. In an embodiment, the one or more humectants can bepresent in an amount from about 1% to about 30%, preferably from about2% to about 15%, and more preferably from about 3% to about 10% of theink jet ink composition.

As discussed, the thermal ink jet ink composition of the inventionincludes one or more binder resins. Any suitable binder resin, solubleor dispersible, can be employed, preferably a solvent soluble binderresin. In an embodiment, the thermal ink jet ink composition of theinvention includes one or more binder resins selected from the groupconsisting of polyamide resins, polyurethane resins, rosin ester resins,acrylic resins, polyvinyl butyral resins, polyesters, polyurethanes,phenolic resins, polyimides, vinyl resins, ethylene vinyl acetateresins, polystyrene/acrylates, cellulose ethers, cellulose nitrateresins, polymaleic anhydrides, acetal polymers, polystyrene/butadienes,polystyrene/methacrylates, sulfonated polyesters, aldehyde resins, andpolyketone resins, and any combination thereof, and preferably one ormore binder resins selected from the group consisting of polyamideresins, rosin ester resins, acrylic resins, polyketone resins, and anycombination thereof. An example of a suitable polyamide resin is ARIZONA201-150™ available from Arizona Chemical Company, Jacksonville, Fla., orCOGNIS VERSAMID 756™, available from Cognis GmbH, Monheim am Rhein,Germany, both of which are alcohol-soluble polyamide resins. Examples ofwood rosin ester resins include UNIREZ™ 8115, available as a 40%solution in ethanol from Penn Color, Doylestown, Pa., which is ahydrogenated wood rosin ester, and STAYBELITE™ ESTER 10, available fromChem Central Corporation. Examples of cellulose nitrate resins areNOBEL™ DLX 3-5 or NOBEL™ DHX 5-8, available from Nobel Enterprises.Examples of polyvinyl butyral resins are PIOLOFORM™ BN18, available fromWacker Chemie AG, and MOWITAL™ B20H available from Kuraray America, Inc.

The binder resin can be present in any suitable amount, for example, inan amount from about 0.1 to about 30%, preferably from about 0.2 toabout 15%, and more preferably from about 0.3 to about 8% of the ink jetink composition.

In a particular embodiment of the thermal ink jet ink composition of theinvention, the volatile organic solvent or solvents can be present in anamount from about 50% to about 95% by weight, the colorant(s) (dyes,pigments, or a combination thereof), can be present in amount from about1% to about 8% by weight, the glycol ether can be present in an amountfrom about 3% to 30% by weight, and the binder resin can be present inan amount from about 1% to about 15% by weight of the ink jet inkcomposition.

The thermal ink jet ink composition of the invention can further includeone or more additives such as surfactants, plasticizers, or conductivesalts. Preferably, a polymeric surfactant is employed. Examples ofsurfactants include siloxanes, silicones, silanols,polyoxyalkyleneamines, propoxylated (poly(oxypropylene)) diamines, alkylether amines, nonyl phenol ethoxylates, ethoxylated fatty amines,quaternized copolymers of vinylpyrrolidone and dimethyl aminoethylmethacrylate, fluorinated organic acid diethanolamine salts, alkoxylatedethylenediamines, polyethylene oxides, polyoxyalkylene polyalkylenepolyamines amines, polyoxyalkylene polyalkylene polyimines, alkylphosphate ethoxylate mixtures, polyoxyalkylene derivatives of propyleneglycol, and polyoxyethylated fatty alcohols. A specific example of asuitable polymeric surfactant, e.g., Silicone Fluid SF-69, availablefrom Dow Corning Co, Midland, Mich., which is a blend of silanols andcyclic silicones. Additional examples of polymeric surfactants includeDISPERSYBYK™ (BYK-Chemie, USA), SOLSPERSE SOLSPERSE™ 13940 which is apolymer/fatty acid condensation polymer) and EFKA™ (EFKA Chemicals)polymeric dispersants.

In any of the embodiments of the invention, the surfactant can bepresent in an amount from about 0.01 to about 1.0%, preferably fromabout 0.01 to about 0.5%, and more preferably from about 0.01 to about0.1% of the ink jet ink composition.

Examples of suitable plasticizers include phthalate plasticizers, e.g.,alkyl benzyl phthalates, butyl benzyl phthalate, dioctyl phthalate,diisobutyl phthalate, dicyclohexyl phthalate, diethyl phthalate,dimethyl isophthalate, dibutyl phthalate, and dimethyl phthalate, esterssuch as di-(2-ethylhexy)-adipate, diisobutyl adipate, glyceroltribenzoate, sucrose benzoate, polypropylene glycol dibenzoate,neopentyl glycol dibenzoate, dibutyl sebacate, andtri-n-hexyltrimellitate, and sulfonamide plasticizers such asPlasticizer 8, available from Monsanto Co., St. Louis, Mo., which isn-ethyl o,p-toluene sulfonamide.

In embodiments of the invention, the plasticizer can be present in anamount from about 0.1 to about 5.0%, preferably from about 0.3 to about3.0%, and more preferably from about 0.5 to about 2.0% of the ink jetink composition.

The thermal ink jet ink composition of the invention may includeadditional ingredients such as surfactants, bactericides, fungicides,algicides, sequestering agents, buffering agents, corrosion inhibitors,antioxidants, light stabilizers, anti-curl agents, thickeners, and otheragents known in the relevant art. In an embodiment, the ink compositionof the invention is free or substantially free of antioxidants.

The thermal ink jet ink composition of the invention has one or moreattractive features such as short unassisted dry times of printedalphanumeric or graphic images, long decap times, good adhesion tosemi-porous and non-porous substrates, and safety or materialcompatibility with one or more components of a thermal ink jet printer.For example, embodiments of the thermal ink jet ink composition of theinvention have a dry time of about 10 seconds or less, such as 7 secondsor less, 4 seconds or less, or 2 seconds or less, under ambientconditions. On porous substrates, the dry times are shorter than insemi- or non-porous substrates. For example, embodiments of the thermalink jet ink composition of the invention have a dry time of about 1second on porous substrates and less than about 5 seconds, preferablyless than about 2 seconds, and more preferably less than about 1 secondon semi-porous substrates.

The thermal ink jet ink composition of the invention can have anysuitable viscosity or surface tension. In embodiments of the invention,the thermal ink jet ink composition has a viscosity of less than about10 cPs, preferably less than about 5 cPs, and more preferably less thanabout 3 cPs, for example, a viscosity from about 1 to 4 or from about 1to about 3 cPs at 25° C.

In embodiments of the invention, the thermal ink jet ink composition hasa surface tension from about 20 to about 50 mN/m, from about 21 to about40 mN/m, or from about 22 to about 30 mN/m at 25° C.

The thermal ink jet ink composition of the invention can be prepared byany suitable method. For example, the chosen ingredients can be combinedand mixed with adequate stirring and the resulting fluid filtered toremove any undissolved impurities.

The present invention further provides a method for printing images on asubstrate in a thermal ink jet printer comprising directing a stream ofdroplets of any of the embodiments of the thermal ink jet inkcomposition of the invention to a substrate and allowing the inkdroplets to dry, thereby printing images on a substrate. Any suitablesubstrate can be printed in accordance with the invention. Examples ofsuitable substrates include porous substrates such as uncoated paper,semi-porous substrates such as aqueous coated paper, clay coated paper,silica coated paper, UV overcoated paper, polymer overcoated paper, andvarnish overcoated paper, and non-porous substrates such as hardplastics, polymer films, metals, glass, and ceramics. The papersubstrates can be thin sheets of paper, rolls of paper, or cardboard.Plastics, metals, glass, and ceramic substrates can be in any suitableform such as in the form of bottles or containers, plates, rods,cylinders, etc.

Examples of polymer coating include a coating of polystyrene, polyvinylalcohol, polyacryate, polymethacrylate, polystryrene or polyvinylchloride. Examples of polymer film substrates include polyvinylbutyrals, polyolefins, polyvinyl chloride, polyethylene terephthalate,PETG, polybutylene terephthalate (PBT), polyester, polycarbonate,acrylonitrile-butadiene-styrene (ABS) copolymer, polyvinyl fluoridepolymer, polyamides, polyimides, and cellulose. Plastics can be treatedplastics (e.g. chemical etch, corona discharge, flame plasma, etc.) oruntreated plastics. Examples of metals include aluminum, copper,stainless steel, and metal alloys. Examples of ceramics include oxides,nitrides, and carbides of metals.

The following examples further illustrate the invention but, of course,should not be construed as in any way limiting its scope.

EXAMPLE 1

This example illustrates embodiments of the thermal ink jet inkcomposition of the invention. The materials employed in preparing theink jet ink composition, their amounts, and the formulation numbers areset forth in Table 1 below.

TABLE 1 Ink formulations in accordance with embodiments of the inventionMaterial 2520 2538 5521 5678 5745 5750 5762 5798 5815 5817 5818 ethanol86.55 45.35 45.49 25.00 85.49 41.50 86.00 86.00 isopropanol 73.451-propanol 79.00 1-butanol 82.28 methanol 41.00 glycol ether PM 10.505.00 3.15 3.50 45.10 40.00 50.00 10.00 10.00 10.00 10.00 Valifast Black4.00 4.00 4.00 4.00 4.00 4.00 4.00 3808 Orasol Black RLI 5.00 ValifastOrange 1.06 1.00 1.00 1.00 3210 Orient Oil Pink 1.38 1.40 312 40% Unirez8115 12.00 12.00 12.08 in EtOH 20% Arizona 20.00 201-150 in EtOH 40%Cognis 7.50 Versamid 756 in EtOH Nobel DLX 3-5 3.00 Piloform LL 41403.00 Joncryl 682 6.00 K-Plast 1022 3.00 Silicone fluid 0.05 0.05 0.050.05 0.01 0.01 0.01 0.01 0.01 SF69 Plasticizer 8 0.50 0.50 1.00 0.500.50

EXAMPLE 2

This Example illustrates the ink dry times of embodiments of the thermalink jet ink composition of the invention.

TABLE 2 Ink dry times of embodiments of the ink composition on varioussubstrates Formulation Unassisted Dry Number Substrate Type Time, sec5678 Clay Coat semi-porous 1 Aqueous Coat semi-porous 2 Varnish Coatsemi-porous 2 UV Coat semi-porous 3 HDPE non-porous 1 Polypropylenenon-porous 2 PET non-porous 1 PVC non-porous 2 Glass non-porous 2Aluminum non-porous 1 5750 Clay Coat semi-porous 1 Aqueous Coatsemi-porous 1 Varnish Coat semi-porous 1 UV Coat semi-porous 2 HDPEnon-porous 2 Polypropylene non-porous 3 PET non-porous 2 PVC non-porous2 Glass non-porous 2 Aluminum non-porous 2 5798 Clay Coat semi-porous 1Aqueous Coat semi-porous 1 Varnish Coat semi-porous 1 UV Coatsemi-porous 2 HDPE non-porous 2 Polypropylene non-porous 3 PETnon-porous 2 PVC non-porous 2 Glass non-porous 1 Aluminum non-porous 1

EXAMPLE 3

This Example illustrates some of the properties of embodiments of theink jet ink composition of the invention.

TABLE 3 Properties of embodiments of the thermal ink jet ink compositionof the invention Formulation Viscosity Surface Tension No. (cPs) (mN/m)5521 3.42 24.1 5678 1.71 22.6 5745 3.10 24.4 5750 3.28 25.0 2520 3.0322.0 5798 1.50 22.6 5815 2.31 20.2

EXAMPLE 4

This Example illustrates the adhesion of the printed images obtainedfrom embodiments of the ink jet ink composition of the invention. Theink jet ink composition Nos. 2520, 5745, 5750 and 5815 produce images onclay coat substrates having aqueous overcoat, UV overcoat, or varnishovercoat, as well as on polyethylene, polypropylene, polystyrene,polyvinyl chloride, polyethylene terephthalate, glass and aluminumsubstrates, that pass a 1 minute rub resistance test as well as a 24hour scratch adhesion test

All references, including publications, patent applications, andpatents, cited herein are hereby incorporated by reference to the sameextent as if each reference were individually and specifically indicatedto be incorporated by reference and were set forth in its entiretyherein.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the invention (especially in the context of thefollowing claims) are to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. The terms “comprising,” “having,” “including,” and “containing”are to be construed as open-ended terms (i.e., meaning “including, butnot limited to,”) unless otherwise noted. Recitation of ranges of valuesherein are merely intended to serve as a shorthand method of referringindividually to each separate value falling within the range, unlessotherwise indicated herein, and each separate value is incorporated intothe specification as if it were individually recited herein. All methodsdescribed herein can be performed in any suitable order unless otherwiseindicated herein or otherwise clearly contradicted by context. The useof any and all examples, or exemplary language (e.g., “such as”)provided herein, is intended merely to better illuminate the inventionand does not pose a limitation on the scope of the invention unlessotherwise claimed. No language in the specification should be construedas indicating any non-claimed element as essential to the practice ofthe invention.

Preferred embodiments of this invention are described herein, includingthe best mode known to the inventors for carrying out the invention.Variations of those preferred embodiments may become apparent to thoseof ordinary skill in the art upon reading the foregoing description. Theinventors expect skilled artisans to employ such variations asappropriate, and the inventors intend for the invention to be practicedotherwise than as specifically described herein. Accordingly, thisinvention includes all modifications and equivalents of the subjectmatter recited in the claims appended hereto as permitted by applicablelaw. Moreover, any combination of the above-described elements in allpossible variations thereof is encompassed by the invention unlessotherwise indicated herein or otherwise clearly contradicted by context.

The invention claimed is:
 1. A thermal ink jet ink compositioncomprising: one or more volatile organic solvents, wherein the one ormore volatile organic solvents are selected from C₁-C₄ alcohols, C₃-C₆ketones, C₄-C₈ ethers, C₃-C₆ esters, and mixtures thereof; one or morehumectants, wherein the humectants are present in an amount not morethan 30% by weight of the ink jet ink composition; one or more binderresins; one or more dyes, a surfactant selected from siloxanes,silicones, silanols, polyoxyalkyleneamines, propoxylated(poly(oxypropylene)) diamines, alkyl ether amines, nonyl phenolethoxylates, ethoxylated fatty amines, quaternized copolymers ofvinylpyrrolidone and dimethyl aminoethyl methacrylate, fluorinatedorganic acid diethanolamine salts, alkoxylated ethylenediamines,polyethylene oxides, polyoxyalkylene polyalkylene polyamines,polyoxyalkylene polyalkylene polyimines, alkyl phosphate ethoxylatemixtures, polyoxyalkylene derivatives of propylene glycol,polyoxyethylated fatty alcohols, and mixtures thereof; a plasticizerselected from ester plasticizers, sulfonamide plasticizers, and mixturesthereof; and optionally water up to 10% by weight of the ink jet inkcomposition, wherein the thermal ink composition is suitable for use inthermal ink jet printers.
 2. The thermal ink jet ink composition ofclaim 1, wherein the ink jet ink composition comprises a plasticizerselected from diisobutyl adipate, glycerol tribenzoate, sucrosebenzoate, polypropylene glycol dibenzoate, neopentyl glycol dibenzoate,dibutyl sebacate, tri-n-hexyltrimellitate, n-ethyl o,p-toluenesulfonamide, and mixtures thereof.
 3. The thermal ink jet inkcomposition of claim 2, wherein the ink jet ink composition comprisesn-ethyl o,p-toluene sulfonamide.
 4. The thermal ink jet ink compositionof claim 1, wherein the ink jet ink composition comprises a polymericsurfactant.
 5. The thermal ink jet ink composition of claim 1, whereinthe ink jet ink composition comprises a surfactant selected fromsiloxanes, silicones, silanols, and mixtures thereof.
 6. The thermal inkjet ink composition of claim 1, wherein the thermal ink jet inkcomposition has a dry time of 4 seconds or less when used in a thermalink jet print head.
 7. The thermal ink jet ink composition of claim 1,wherein the one or more volatile organic solvents are selected frommethanol, ethanol, 1-propanol, acetone, methyl ethyl ketone, methylacetate, ethyl acetate, n-butyl acetate, and mixtures thereof.
 8. Thethermal ink jet ink composition of claim 7, wherein the one or morevolatile organic solvents are selected from methanol, ethanol, methylethyl ketone, and mixtures thereof.
 9. The thermal ink jet inkcomposition of claim 8, wherein the one or more volatile organicsolvents comprises methyl ethyl ketone.
 10. The thermal ink jet inkcomposition of claim 8, wherein the one or more volatile organicsolvents comprises ethanol.
 11. The thermal ink jet ink composition ofclaim 1 wherein the one or more volatile organic solvents are present inan amount from 50% to 95% by weight of the ink jet ink composition. 12.The thermal ink jet ink composition of claim 1, wherein the one or morehumectants are selected from glycol ether, diacetone alcohol, andmixtures thereof.
 13. The thermal ink jet ink composition of claim 1,wherein the one or more binder resins are selected from polyamideresins, polyurethane resins, rosin ester resins, acrylic resins,polyvinyl butyral resins, polyester resins, polyurethane resins,phenolic resins, polyimide resins, vinyl resins, ethylene vinyl acetateresins, polystyrene/acrylate resins, cellulose ethers, cellulose nitrateresins, polymaleic anhydride resins, acetal polymers,polystyrene/butadiene resins, polystyrene/methacrylate resins,sulfonated polyester resins, aldehyde resins, polyketone resins, andmixtures thereof.
 14. The thermal ink jet ink composition of claim 13,wherein the one or more binder resins are selected from rosin esterresins, acrylic resins, polyvinyl butyral resins, vinyl resins,polystyrene/acrylate resins, cellulose nitrate resins,polystyrene/methacrylate resins, sulfonated polyester resins, andmixtures thereof.
 15. The thermal ink jet ink composition of claim 1,wherein the one or more dyes are selected from C.I. Solvent Orange 54,C.I. Basic Violet 3, C.I. Basic Violet 4, C.I. Solvent Black 3, C.I.Solvent Black 26, C.I. Solvent Black 27, C.I. Solvent Black 29, andmixtures thereof.
 16. The thermal ink jet ink composition of claim 1,wherein the thermal ink jet ink composition has a viscosity of less than3 cPs at 25° C.
 17. The thermal ink jet ink composition of claim 1,optionally including water up to 5% by weight of the ink jet inkcomposition.
 18. A method for printing images on a substrate with athermal ink jet printer, comprising: providing a thermal ink jet inkcomposition comprising the ink jet ink composition of claim 1; using athermal ink jet print head to direct droplets of the thermal ink jet inkcomposition to a substrate; and allowing the ink droplets to dry,thereby printing images on a substrate.
 19. The method of claim 18,wherein the thermal ink jet ink composition has a dry time of 2 secondsor less.
 20. A thermal ink jet ink composition comprising: one or morevolatile organic solvents, wherein the one or more volatile organicsolvents are selected from C₁-C₄ alcohols, C₃-C₆ ketones, and mixturesthereof; one or more humectants, wherein the humectants are selectedfrom glycol ethers, diacetone alcohol, and mixtures thereof and arepresent in an amount from 2% to 5% by weight of the ink jet inkcomposition; one or more binder resins selected from rosin ester resins,acrylic resins, polyvinyl butyral resins, vinyl resins,polystyrene/acrylate resins, cellulose nitrate resins,polystyrene/methacrylate resins, sulfonated polyester resins, andmixtures thereof, wherein the one or more binder resins are present inan amount from about 0.3% to about 8% by weight of the ink composition;one or more dyes, a surfactant selected from siloxanes, silicones,silanols, polyoxyalkyleneamines, propoxylated (poly(oxypropylene))diamines, alkyl ether amines, nonyl phenol ethoxylates, ethoxylatedfatty amines, quaternized copolymers of vinylpyrrolidone and dimethylaminoethyl methacrylate, fluorinated organic acid diethanolamine salts,alkoxylated ethylenediamines, polyethylene oxides, polyoxyalkylenepolyalkylene polyamines, polyoxyalkylene polyalkylene polyimines, alkylphosphate ethoxylate mixtures, polyoxyalkylene derivatives of propyleneglycol, polyoxyethylated fatty alcohols, and mixtures thereof; aplasticizer selected from ester plasticizers, sulfonamide plasticizers,and mixtures thereof; and optionally water up to 5% by weight of the inkjet ink composition.